This invention relates to a multicolor photographic element having improved latent image keeping and to a method of improving the latent image keeping of a multicolor photographic element.
Stability of silver halide color photographic materials under various storage conditions is an important characteristic, particularly for materials designed for use in consumer markets, where storage conditions may be quite variable. One aspect of this stability is stability of the latent image formed on exposure of the material. Instability of the latent image leads to undesirable changes in the photographic speed of the material as a function of storage after exposure but before processing in a photographic developer. This instability can be particularly troublesome in multilayer color photographic materials if the latent image keeping density changes are variable in the different color records of the multicolor element. This variability can lead to mismatches in the speed and curve shape of the color records. Various materials have been disclosed in the prior art for stabilizing the latent image including N-alkynyl benzothiazoliums (U.S. Pat. No. 4,780,400), N-(2-benzoxazolyl) propargyl amines (U.S. Pat. Nos. 4378426 and 4,451,557), 2-hydroxyamino-1,3,5-triazines, hydroxyamic acids (U.S. Pat. Nos. 4339515 and 4,330,606) and the like. A number of these materials have the characteristic that they diffuse throughout the multilayer photographic element so that the latent image keeping characteristics of the different color records cannot be separately adjusted. In addition, many of these materials function better in blue sensitized layers than in red or green sensitized layers. Consequently, achieving good stability of the latent image, especially in green or red sensitized layers, continues to be a problem in practical color multilayer photographic materials.
It is desirable to find new means to control latent image keeping speed and density changes for multicolor photographic elements. It is particularly desirable to find means that allow the latent image keeping speed and density changes to be adjusted separately in the different color records of the multicolor photographic element.
One aspect of this invention comprises a multicolor photographic element comprising a support bearing a cyan dye image-forming unit comprising at least one red-sensitive silver halide emulsion layer having associated therewith at least one cyan dye-forming coupler, a magenta dye image-forming unit comprising at least one green-sensitive silver halide emulsion layer having associated therewith at least one magenta dye-forming coupler, a yellow dye image-forming unit comprising at least one blue-sensitive silver halide emulsion layer having associated therewith at least one yellow dye-forming coupler, wherein at least one of said red-sensitive or green-sensitive layers comprises a fragmentable electron donating compound of the formula: Xxe2x80x94Yxe2x80x2 or a compound which contains a moiety of the formula xe2x80x94Xxe2x80x94Yxe2x80x2;
wherein the speed gain deriving from addition of said compound to said layer is less than or equal to 0.05 log sensitivity units and wherein
X is an electron donor moiety, Yxe2x80x2 is a leaving proton H or a leaving group Y, with the proviso that if Yxe2x80x2 is a proton, a base, xcex2xe2x88x92, is present in the emulsion layer, and wherein:
1) Xxe2x80x94Yxe2x80x2 has an oxidation potential between 0 and about 1.4 V;
2) the oxidized form of Xxe2x80x94Yxe2x80x2 undergoes a bond cleavage reaction to give the radical Xxc2x7 and the leaving fragment Yxe2x80x2; and
3) the radical Xxc2x7 has an oxidation potential xe2x89xa6xe2x88x920.7V (that is, equal to or more negative than about xe2x88x920.7V).
Another aspect of this invention comprises a method of improving the latent image keeping of a multilayer photographic element comprising a support bearing a cyan dye image-forming unit comprising at least one red-sensitive silver halide emulsion layer having associated therewith at least one cyan dye-forming coupler, a magenta dye image-forming unit comprising at least one green-sensitive silver halide emulsion layer having associated therewith at least one magenta dye-forming coupler, a yellow dye image-forming unit comprising at least one blue-sensitive silver halide emulsion layer having associated therewith at least one yellow dye-forming coupler, wherein for at least one of said red-sensitive or green-sensitive layers, said method comprises adding a fragmentable electron donating compound of the formula: Xxe2x80x94Yxe2x80x2 or a compound which contains a moiety of the formula xe2x80x94Xxe2x80x94Yxe2x80x2, in an amount sufficient to improve the latent image keeping but insufficient to impart a speed gain deriving from addition of said compound to said layer of more than 0.05 log sensitivity units and wherein
X is an electron donor moiety, Yxe2x80x2 is a leaving proton H or a leaving group Y, with the proviso that if Yxe2x80x2 is a proton, a base, xcex2xe2x88x92, is present in the emulsion layer, and wherein:
1) Xxe2x80x94Yxe2x80x2 has an oxidation potential between 0 and about 1.4 V;
2) the oxidized form of Xxe2x80x94Yxe2x80x2 undergoes a bond cleavage reaction to give the radical Xxc2x7 and the leaving fragment Yxe2x80x2; and,
3) the radical Xxc2x7 has an oxidation potential xe2x89xa6xe2x88x920.7V.
This invention provides a multicolor photographic element having little speed or density loss with latent image keeping and latent image keeping characteristics that are well matched between the different color records.
We have found that addition of a small amount of fragmentable two-electron donor to the emulsion layers of a multilayer color photographic element can significantly improve the latent image stability of the material. Fragmentable two electron donors (FED""s) are compounds that have been designed to improve the speed of photographic materials by providing two electrons for each photon absorbed by the silver halide emulsion. Fragmentable electron donating compounds are described in U.S. Pat. Nos. 5,747,235 and 5,747,236 and 5,994,051, 6,010,841, 6,054,260 and 6,153,371, the entire disclosures thereof are incorporated herein by reference. These references disclose speed gains associated with the use of fragmentable two-electron donors in a wide variety of silver halide emulsions. Surprisingly, we have found that, particularly for green and red sensitized emulsions, latent image can be stabilized by use of an amount of fragmentable two-electron donor that gives little or no speed gain when added to the emulsion layer. When the fragmentable two-electron donor is a moiety attached to a silver halide absorptive group or to a sensitizing dye, the additional advantage is obtained that latent image keeping changes can be controlled independently in the different color records of the multicolor element. Independent control of latent image keeping changes in the different layers (fast, mid, or slow) of a given color record is also possible.
One aspect of this invention comprises a multicolor photographic element comprising a support bearing a cyan dye image-forming unit comprising at least one red-sensitive silver halide emulsion layer having associated therewith at least one cyan dye-forming coupler, a magenta dye image-forming unit comprising at least one green-sensitive silver halide emulsion layer having associated therewith at least one magenta dye-forming coupler, a yellow dye image-forming unit comprising at least one blue-sensitive silver halide emulsion layer having associated therewith at least one yellow dye-forming coupler, wherein at least one of said red-sensitive or green-sensitive layers comprises a fragmentable electron donating compound of the formula: Xxe2x80x94Yxe2x80x2 or a compound which contains a moiety of the formula xe2x80x94Xxe2x80x94Yxe2x80x2;
wherein the speed gain deriving from addition of said compound to said layer is less than or equal to 0.05 log sensitivity units and wherein
X is an electron donor moiety, Yxe2x80x2 is a leaving proton H or a leaving group Y, with the proviso that if Yxe2x80x2 is a proton, a base, xcex2xe2x88x92, is present in the emulsion layer, and wherein:
1) Xxe2x80x94Yxe2x80x2 has an oxidation potential between 0 and about 1.4 V;
2) the oxidized form of Xxe2x80x94Yxe2x80x2 undergoes a bond cleavage reaction to give the radical Xxc2x7 and the leaving fragment Yxe2x80x2; and
3) the radical Xxc2x7 has an oxidation potential xe2x89xa6xe2x88x920.7V (that is, equal to or more negative than about xe2x88x920.7V).
In this patent application, oxidation potentials are reported as xe2x80x9cVxe2x80x9d which represents xe2x80x9cvolts versus a saturated calomel reference electrodexe2x80x9d.
In embodiments of the invention in which Yxe2x80x2 is Y, the following represents the reactions are believed to take place when Xxe2x80x94Y undergoes oxidation and fragmentation to produce a radical Xxc2x7, which then undergoes further oxidation. 
where E1 is the oxidation potential of Xxe2x80x94Y and E2 is the oxidation potential of the radical Xxc2x7.
E1 is preferably no higher than about 1.4 V and preferably less than about 1.0 V. The oxidation potential is preferably greater than 0, more preferably greater than about 0.3 V. E1 is preferably in the range of about 0 to about 1.4 V, and more preferably from about 0.3 V to about 1.0 V.
In this invention the oxidation potential, E2, of the radical Xxc2x7 is equal to or more negative than xe2x88x920.7V, preferably more negative than about xe2x88x920.9 V. E2 is preferably in the range of from about xe2x88x920.7 to about xe2x88x922 V, more preferably from about xe2x88x920.8 to about xe2x88x922 V and most preferably from about xe2x88x920.9 to about xe2x88x921.6 V.
The structural features of Xxe2x80x94Y are defined by the characteristics of the two parts, namely the fragment X and the fragment Y. The structural features of the fragment X determine the oxidation potential of the Xxe2x80x94Y molecule and that of the radical Xxc2x7, whereas both the X and Y fragments affect the fragmentation rate of the oxidized molecule Xxe2x80x94Yxc2x7+.
In embodiments of the invention in which Yxe2x80x2 is H, the following represents the reactions believed to take place when the compound Xxe2x80x94H undergoes oxidation and deprotonation to the base, xcex2xe2x88x92, to produce a radical Xxc2x7, which in a preferred embodiment undergoes further oxidation. 
As mentioned above, the base xcex2xe2x88x92 is present in the emulsion. It is specifically contemplated that the base xcex2xe2x88x92 can be in the emulsion by virtue of being covalently linked to X.
Preferred X groups are of the general formula: 
The symbol xe2x80x9cRxe2x80x9d (that is R without a subscript) is used in all structural formulae in this patent application to represent a hydrogen atom or an unsubstituted or substituted alkyl group.
In structure (I):
m=0, 1;
Z=O, S, Se, Te;
Ar=aryl group (e.g., phenyl, naphthyl, phenanthryl, anthryl); or heterocyclic group (e.g., pyridine, indole, benzimidazole, thiazole, benzothiazole, thiadiazole, etc.);
R1=R, carboxyl, amide, sulfonamide, halogen, NR2, (OH)n, (ORxe2x80x2)n, or (SR)n;
Rxe2x80x2=alkyl or substituted alkyl;
n=1-3;
R2=R, Arxe2x80x2;
R3=R, Arxe2x80x2;
R2 and R3 together can form 5- to 8-membered ring;
R2 and Ar=can be linked to form 5- to 8-membered ring;
R3 and Ar=can be linked to form 5- to 8-membered ring;
Arxe2x80x2=aryl group such as phenyl, substituted phenyl, or heterocyclic group (e.g., pyridine, benzothiazole, etc.)
R=a hydrogen atom or an unsubstituted or substituted alkyl group.
In structure (II):
Ar=aryl group (e.g., phenyl, naphthyl, phenanthryl); or heterocyclic group (e.g., pyridine, benzothiazole, etc.);
R4=a substituent having a Hammett sigma value of xe2x88x921 to +1, preferably xe2x88x920.7 to +0.7, e.g., R, OR, SR, halogen, CHO, C(O)R, COOR, CONR2, SO3R, SO2NR2, SO2R, SOR, C(S)R, etc;
R5=R, Arxe2x80x2
R6 and R7=R, Arxe2x80x2
R5 and Ar=can be linked to form 5- to 8-membered ring;
R6 and Ar=can be linked to form 5- to 8-membered ring (in which case, R6 can be a hetero atom);
R5 and R6 can be linked to form 5- to 8-membered ring;
R6 and R7 can be linked to form 5- to 8-membered ring;
Arxe2x80x2=aryl group such as phenyl, substituted phenyl, heterocyclic group;
R=hydrogen atom or an unsubstituted or substituted alkyl group.
A discussion on Hammett sigma values can be found in C. Hansch and R. W. Taft Chem. Rev. Vol 91, (1991) p 165, the disclosure of which is incorporated herein by reference.
In structure (III):
W=O, S, Se;
Ar=aryl group (e.g., phenyl, naphthyl, phenanthryl, anthryl); or heterocyclic group (e.g., indole, benzimidazole, etc.)
R8=R, carboxyl, NR2, (OR)n, or (SR)n (n=1-3);
R9 and R10=R, Arxe2x80x2;
R9 and Ar=can be linked to form 5- to 8-membered ring;
Arxe2x80x2=aryl group such as phenyl substituted phenyl or heterocyclic group;
R=a hydrogen atom or an unsubstituted or substituted alkyl group.
In structure (IV):
xe2x80x9cringxe2x80x9d represents a substituted or unsubstituted 5-, 6- or 7-membered unsaturated ring, preferably a heterocyclic ring.
The following are illustrative examples of the group X of the general structure I: 
In the structures of this patent application a designation such as xe2x80x94OR(NR2) indicates that either xe2x80x94OR or xe2x80x94NR2 can be present.
The following are illustrative examples of the group X of general structure 
Z1=a covalent bond, S, O, Se, NR, CR2, CRxe2x95x90CR, or CH2CH2. 
Z2=S, O, Se, NR, CR2, CRxe2x95x90CR, R13,=alkyl, substituted alkyl or aryl, and R14=H, alkyl substituted alkyl or aryl.
The following are illustrative examples of the group X of the general structure III: 
The following are illustrative examples of the group X of the general structure IV: 
Preferred Yxe2x80x2 groups are:
(1) Xxe2x80x2, where Xxe2x80x2 is an X group as defined in structures I-IV and may be the same as or different from the X group to which it is attached
(2) xe2x80x94cooxe2x88x92
(3) xe2x80x94M(Rxe2x80x2)3 
where M=Si, Sn or Ge; and Rxe2x80x2=alkyl or substituted alkyl
(4) xe2x80x94Bxe2x88x92(Arxe2x80x3)3 
where Arxe2x80x3=aryl or substituted aryl
(5) xe2x80x94H
In preferred embodiments of this invention Yxe2x80x2 is xe2x80x94H, xe2x80x94COOxe2x88x92 or xe2x80x94Si(Rxe2x80x2)3 or xe2x80x94Xxe2x80x2. Particularly preferred Yxe2x80x2 groups are xe2x80x94H, xe2x80x94COOxe2x88x92 or xe2x80x94Si(Rxe2x80x2)3.
In embodiments of the invention in which Yxe2x80x2 is a proton, a base, xcex2xe2x88x92, is present in the emulsion layer and may be covalently linked directly or indirectly to X. The base is preferably the conjugate base of an acid of pKa between about 1 and about 8, preferably about 2 to about 7. Collections of pKa values are available (see, for example: Dissociation Constants of Organic Bases in Aqueous Solution, D. D. Perrin (Butterworths, London, 1965), CRC Handbook of Chemistry and Physics, 77th ed, D. R. Lide (CRC Press, Boca Raton, Fla., 1996)). Examples of useful bases are included in Table I.
Preferably the base, xcex2xe2x88x92 is a carboxylate, sulfate or amine oxide.
In preferred embodiments of the invention, the fragmentable electron donating compound contains a light absorbing group, Z, which is attached directly or indirectly to X, a silver halide absorptive group, A, directly or indirectly attached to X, or a chromophore forming group, Q, which is attached to X. Such fragmentable electron donating compounds are preferably of the following formulae: 
Z is a light absorbing group;
k is 1 or 2;
A is a silver halide adsorptive group that preferably contains at least one atom of N, S, P, Se, or Te that promotes adsorption to silver halide;
L represents a linking group containing at least one C, N, S, P or O atom; and
Q represents the atoms necessary to form a chromophore comprising an amidinium-ion, a carboxyl-ion or dipolar-amidic chromophoric system when conjugated with Xxe2x80x94Yxe2x80x2.
Z is a light absorbing group including, for example, cyanine dyes, complex cyanine dyes, merocyanine dyes, complex merocyanine dyes, homopolar cyanine dyes, styryl dyes, oxonol dyes, hemioxonol dyes, and hemicyanine dyes.
Preferred Z groups are derived from the following dyes: 
The linking group L may be attached to the dye at one (or more) of the heteroatoms, at one (or more) of the aromatic or heterocyclic rings, or at one (or more) of the atoms of the polymethine chain. For simplicity, and because of the multiple possible attachment sites, the attachment of the L group is not specifically indicated in the generic structures.
The silver halide adsorptive group A is preferably a silver-ion ligand moiety or a cationic surfactant moiety. In preferred embodiments, A is selected from the group consisting of: i) sulfur acids and their Se and Te analogs, ii) nitrogen acids, iii) thioethers and their Se and Te analogs, iv) phosphines, v) thionamides, selenamides, and telluramides, and vi) carbon acids.
Illustrative A groups include: 
The point of attachment of the linking group L to the silver halide adsorptive group A will vary depending on the structure of the adsorptive group, and may be at one (or more) of the heteroatoms, at one (or more) of the aromatic or heterocyclic rings.
The linkage group represented by L which connects the light absorbing group to the fragmentable electron donating group XY by a covalent bond is preferably an organic linking group containing a least one C, N, S, or O atom. It is also desired that the linking group not be completely aromatic or unsaturated, so that a pi-conjugation system cannot exist between the Z and XY moieties. Preferred examples of the linkage group include, an alkylene group, an arylene group, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94Cxe2x95x90O, xe2x80x94SO2xe2x80x94, xe2x80x94NHxe2x80x94, xe2x80x94Pxe2x95x90O, and xe2x80x94Nxe2x95x90. Each of these linking components can be optionally substituted and can be used alone or in combination. Examples of preferred combinations of these groups are: 
The length of the linkage group can be limited to a single atom or can be much longer, for instance up to 30 atoms in length. A preferred length is from about 2 to 20 atoms, and most preferred is 3 to 10 atoms. Some preferred examples of L can be represented by the general formulae indicated below: 
Q represents the atoms necessary to form a chromophore comprising an amidinium-ion, a carboxyl-ion or dipolar-amidic chromophoric system when conjugated with Xxe2x80x94Yxe2x80x2. Preferably the chromophoric system is of the type generally found in cyanine, complex cyanine, hemicyanine, merocyanine, and complex merocyanine dyes as described in F. M. Hamer, The Cyanine Dyes and Related Compounds (Interscience Publishers, New York, 1964).
Illustrative Q groups include: 
Particularly preferred are Q groups of the formula: 
wherein:
X2 is O, S, N, or C(R19)2, where R19 is substituted or unsubstituted alkyl.
each R17 is independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or substituted or unsubstituted aryl group,
a is an integer of 1-4;
and
R18 is substituted or unsubstituted alkyl, or substituted or unsubstituted aryl.
Illustrative fragmentable electron donating compounds include: 
Fragmentable electron donating compounds are described more fully in U.S. Pat. Nos. 5,747,235 and 5,747,236 and 5,994,051, 6,010,841, 6,054,260 and 6,153,371, the entire disclosures thereof are incorporated herein by reference.
In addition, it is also contemplated to use protected fragmentable electron donors in the practice of this invention. Protected fragmentable electron donors comprise compounds of formula (a), (b) or (c):
xcex94xe2x80x94(t)mxe2x80x94XYxe2x80x2xe2x80x83xe2x80x83(a)
XYxe2x80x2xe2x80x94(t)mxe2x80x94xcex94xe2x80x83xe2x80x83(b)
xcex94xe2x80x94(t)mxe2x80x94XYxe2x80x2xe2x80x94(t)mxe2x80x94xcex94xe2x80x83xe2x80x83(c)
wherein xcex94 is protective group that is eliminated in the coating environment, t is a timing group, m is an integer from 0 to 3, and XYxe2x80x2 is a fragmentable electron donor moiety in which X is an electron donor group and Yxe2x80x2 is a leaving proton H or a leaving group Y, with the proviso that if Yxe2x80x2 is a proton, a base, xcex2xe2x88x92 is present in the emulsion or is covalently linked directly or indirectly to X, and XYxe2x80x2 is a fragmentable electron donor moiety as defined above.
The protective group xcex94 is eliminated by components in the coating environment such as hydroxyl ion. The scission mechanism thereof includes, for example, a direct scission, such as intermolecular nucleophilic substitution reaction or elimination reaction, and an indirect breaking, such as intermolecular addition reaction or intramolecular nucleophilic substitution reaction. Examples of the protective group represented by xcex94 include a group cleaving on hydrolysis (e.g., acyl group, sulfonyl group, sulfinyl group, aminomethyl group), a group cleaving on reverse Michael addition reaction (e.g., 2-cyanoethyl group, 2-acylethyl group, 2-sulfonylethyl group, 2-carbamoylethyl group, pyrrolidine-2,5-dioxo-3-yl group), a group cleaving on intramolecular nucleophilic substitution reaction, a group blocked with a phthalide group or a saccharin group and a group blocked with an imidomethyl group. Protected fragmentable electron donor compounds are described more fully in co-pending application U.S. Serial No. 09/750,855 filed Dec. 28, 2000, the disclosure of which is incorporated here by reference.
The fragmentable electron donating sensitizer compounds of the present invention can be included in a silver halide emulsion by direct dispersion in the emulsion, or they may be dissolved in a solvent such as water, methanol or ethanol for example, or in a mixture of such solvents, and the resulting solution can be added to the emulsion. The compounds of the present invention may also be added from solutions containing a base and/or surfactants, or may be incorporated into aqueous slurries or gelatin dispersions and then added to the emulsion.
The amount of fragmentable electron donating compound which is employed in this invention may range from as little as 1xc3x9710xe2x88x929 mole to as much as about 0.1 mole per mole of silver in an emulsion layer, preferably from as little as 5xc3x9710xe2x88x929 mole to as much as about 0.01 mole per mole of silver in an emulsion layer. Where the oxidation potential E1 for the XY moiety of the electron donating compound is a relatively low potential, it is more active, and relatively less of the FED compound need be employed. Conversely, where the oxidation potential for the XY moiety of the electron donating compound is relatively high, a larger amount thereof, per mole of silver, is employed. In addition, for XY moieties that have silver halide adsorptive groups A or light absorptive groups Z or chromophoric groups Q directly or indirectly attached to X, the fragmentable electron donating compound is more closely associated with the silver halide grain and relatively less of the FED compound need be employed. In any case, for the practice of this invention in green and red sensitized layers of a multicolor film element, the amount of fragmentable electron donating compound to be used must be adjusted to give a speed gain that is less than or equal to 0.05 log sensitivity units.
Various compounds may be added to the photographic material of the present invention for the purpose of lowering the fogging of the material during manufacture, storage, or processing. Typical antifoggants are discussed in Section VI of Research Disclosure Sep. 1996, Number 389, Item 38957, which will be identified hereafter by the term xe2x80x9cResearch Disclosure I.xe2x80x9d The Sections hereafter referred to are Sections of the Research Disclosure I unless otherwise indicated. All Research Disclosures referenced are published by Kenneth Mason Publications, Ltd., Dudley Annex, 12a North Street, Emsworth, Hampshire PO10 7DQ, ENGLAND., Such antifoggants include, for example tetraazaindenes, mercaptotetrazoles, polyhydroxybenzenes, hydroxyaminobenzenes, combinations of a thiosulfonate and a sulfinate, and the like.
For this invention, polyhydroxybenzene and hydroxyaminobenzene compounds (hereinafter xe2x80x9chydroxybenzene compoundsxe2x80x9d) are preferred as they are effective for lowering fog without decreasing the emulsion sensitvity. Examples of hydroxybenzene compounds are: 
In these formulae, V and Vxe2x80x2 each independently represent xe2x80x94H, xe2x80x94OH, a halogen atom, xe2x80x94OM (M is alkali metal ion), an alkyl group, a phenyl group, an amino group, a carbonyl group, a sulfone group, a sulfonated phenyl group, a sulfonated alkyl group, a sulfonated amino group, a carboxyphenyl group, a carboxyalkyl group, a carboxyamino group, a hydroxyphenyl group, a hydroxyalkyl group, an alkylether group, an alkylphenyl group, an alkylthioether group, or a phenylthioether group.
More preferably, they each independently represent xe2x80x94H, xe2x80x94OH, xe2x80x94Cl, xe2x80x94Br, xe2x80x94COOH, xe2x80x94CH2CH2COOH, xe2x80x94CH3, xe2x80x94CH2CH3, xe2x80x94C(CH3)3, xe2x80x94OCH3, xe2x80x94CHO, xe2x80x94SO3K, xe2x80x94SO3Na, xe2x80x94SO3H, xe2x80x94SCH3, or -phenyl.
Especially preferred hydroxybenzene compounds follow: 
Hydroxybenzene compounds may be added to the emulsion layers or any other layers constituting the photographic material of the present invention. The preferred amount added is from 1xc3x9710xe2x88x923 to 1xc3x9710xe2x88x921 mol, and more preferred is 1xc3x9710xe2x88x923 to 2xc3x9710xe2x88x922 mol, per mol of silver halide.
The emulsion layer of the photographic element of the invention can comprise any one or more of the light sensitive layers of the photographic element. The photographic elements made in accordance with the present invention are multicolor elements. Multicolor elements contain dye image-forming units sensitive to each of the three primary regions of the spectrum. Each unit can be comprised of a single emulsion layer or of multiple emulsion layers sensitive to a given region of the spectrum. The layers of the element, including the layers of the image-forming units, can be arranged in various orders as known in the art.
A typical multicolor photographic element comprises a support bearing a cyan dye image-forming unit comprised of at least one red-sensitive silver halide emulsion layer having associated therewith at least one cyan dye-forming coupler, a magenta dye image-forming unit comprising at least one green-sensitive silver halide emulsion layer having associated therewith at least one magenta dye-forming coupler, and a yellow dye image-forming unit comprising at least one blue-sensitive silver halide emulsion layer having associated therewith at least one yellow dye-forming coupler. The element can contain additional layers, such as filter layers, interlayers, overcoat layers, subbing layers, and the like. All of these can be coated on a support which is preferably transparent.
Image dye forming couplers that can be used in the multilayer photographic element of the incention include, for example:
Couplers which combine with oxidized developer to produce cyan colored dyes are shown, for example, in Weissberger et al U.S. Pat. No. 2,474,293, Vittum et al U.S. Pat. No. 3,002,836, Stecker U.S. Pat. No. 3,041,236, Ono et al U.S. Pat. No. 4,746,602, Kilminster U.S. Pat. No. 4,753,871, Aoki et al U.S. Pat. No. 4,770,988, Kilminster et al U.S. Pat. No. 4,775,616, Hamada et al U.S. Pat. No. 4,818,667, Masukawa et al U.S. Pat. No. 4,818,672, Monbaliu et al U.S. Pat. No. 4,822,729, Monbaliu et al U.S. Pat. No. 4,839,267, Masukawa et al U.S. Pat. No. 4,840,883, Hoke et al U.S. Pat. No. 4,849,328, Miura et al U.S. Pat. No. 4,865,961, Tachibana et al U.S. Pat. No. 4,873,183, Shimada et al U.S. Pat. No. 4,883,746, Tani et al U.S. Pat. No. 4,900,656, Ono et al U.S. Pat. No. 4,904,575, Tachibana et al U.S. Pat. No. 4,916,051, Nakayama et al U.S. Pat. No. 4,921,783, Merkel et al U.S. Patent 4,923,791, Tachibaba et al U.S. Pat. No. 4,950,585, Aoki et al U.S. Pat. No. 4,971,898, Lau U.S. Pat. No. 4,990,436, Masukawa et al U.S. Pat. No. 4,996,139, Merkel U.S. Pat. No. 5,008,180, Wolff U.S. Pat. No. 5,015,565, Tachibana et al U.S. Pat. No. 5,011,765, Kida et al U.S. Pat. No. 5,011,766, Masukawa et al U.S. Pat. No. 5,017,467, Hoke U.S. Pat. No. 5,045,442, Uchida et al U.S. Pat. No. 5,051,347, Kaneko U.S. Pat. No. 5,061,613, Kitaet al U.S. Pat. No. 5,071,737, Langen et al U.S. Pat. No. 5,075,207, Fukunada et al U.S. Pat. No. 5,091,297, Tsukahara et al U.S. Pat. No. 5,094,938, Shimada et al U.S. Pat. No. 5,104,783, Fujita et al U.S. Pat. No. 5,178,993, Naito et al U.S. Pat. No. 5,813,729, Ikesu et al U.S. Pat. No. 5,187,057, Tsukahara et al U.S. Pat. No. 5,192,651, Schumann et al U.S. Pat. No. 5,200,305, Yamakawa et al U.S. Pat. No. 5,202,224, Shimada et al U.S. Pat. No. 5,206,130, Ikesu et al U.S. Pat. No. 5,208,141, Tsukahara et al U.S. Pat. No. 5,210,011, Sato et al U.S. Pat. No. 5,215,871, Kita et al U.S. Pat. No. 5,223,386, Sato et al U.S. Pat. No. 5,227,287, Suzuki et al U.S. Pat. No. 5,256,526, Kobayashi et al U.S. Pat. No. 5,258,270, Shimada et al U.S. Pat. No. 5,272,051, Ikesu et al U.S. Pat. No. 5,306,610, Yamakawa U.S. Pat. No. 5,326,682, Shimada et al U.S. Pat. No. 5,366,856, Naruse et al U.S. Pat. No. 5,378,596, Takizawa et al U.S. Pat. No. 5,380,638, Lau et al U.S. Pat. No. 5,382,502, Matsuoka et al U.S. Pat. No. 5,384,236, Takada et al U.S. Pat. No. 5,397,691, Kaneko et al U.S. Pat. No. 5,415,990, Asami U.S. Pat. No. 5,434,034, Tang et al U.S. Pat. No. 5,441,863, Tashiro et al EPO 0 246 616, Lau EPO 0 250 201, Kilminster et al EPO 0 271 323, Sakanoue et al EPO 0 295 632, Mihayashi et al EPO 0 307 927, Ono et al EPO 0 333 185, Shinba et al EPO 0 378 898, Giusto EPO 0 389 817, Sato et al EPO 0 487 111, Suzuki et al EPO 0 488 248, Ikesu et al EPO 0 539 034, Suzuki et al EPO 0 545 300, Yamakawa et al EPO 0 556 700, Shimada et al EPO 0 556 777, Kawai EPO 0 556 858, Yoshioka EPO 0 569 979, Ikesu et al EPO 0 608 133, Merkel et al EPO 0 636 936, Merkel et al EO 0 651 286, Sugita et al EPO 0 690 344, Renner et al German OLS 4,026,903, Langen et al German OLS 3,624,777 and Wolff et al German OLS 3,823,049, Magenta coupler types are shown, for example, in Porter et al U.S. Pat. Nos. 2,311,082 and 2,369,489, Tuite U.S. Pat. No. 3,152,896, Arai et al U.S. Pat. No. 3,935,015, Renner U.S. Pat. No. 4,745,052, Ogawa et al U.S. Pat. No. 4,762,775, Kida et al U.S. Pat. No. 4,791,052, Wolff et al U.S. Pat. No. 4,812,576, Wolff et al U.S. Pat. No. 4,835,094, Abe et al U.S. Pat. No. 4,840,877, Wolff U.S. Pat. No. 4,845,022, Krishnamurthy et al U.S. Pat. No. 4,853,319, Renner U.S. Pat. No. 4,868,099, Helling et al U.S. Pat. No. 4,865,960, Normandin U.S. Pat. No. 4,871,652, Buckland U.S. Pat. No. 4,876,182, Bowne et al U.S. Pat. No. 4,892,805, Crawley et al U.S. Pat. No. 4,900,657, Furutachi U.S. Pat. No. 4,910,124, Ikesu et al U.S. Pat. No. 4,914,013, Yokoyama et al U.S. Pat. No. 4,921,968, Furutachi et al U.S. Pat. No. 4,929,540, Kim et al U.S. Pat. No. 4,933,465, Renner U.S. Pat. No. 4,942,116, Normandin et al U.S. Pat. No. 4,942,117, Normandin et al U.S. Pat. No. 4,942,1 18, Normandin et al U.S. Pat. No. 4,959,480, Shimazaki et al U.S. Pat. No. 4,968,594, Ishige et al U.S. Pat. No. 4,988,614, Bowne et al U.S. Pat. No. 4,992,361, Renner et al U.S. Pat. No. 5,002,864, Bums et al U.S. Pat. No. 5,021,325, Sato et al U.S. Pat. No. 5,066,575, Morigaki et al U.S. Pat. No. 5,068,171, Ohya et al U.S. Pat. No. 5,071,739, Chen et al U.S. Pat. No. 5,100,772, Harder et al U.S. Pat. No. 5,110,942, Kimura et al U.S. Pat. No. 5,116,990, Yokoyama et al U.S. Pat. No. 5,118,812, Kunitz et al U.S. Pat. No. 5,134,059, Mizukawa et al U.S. Pat. No. 5,155,016, Romanet et al U.S. Pat. No. 5,183,728, Tang et al U.S. Pat. No. 5,234,805, Sato et al U.S. Pat. No. 5,235,058, Krishnarnurthy et al U.S. Pat. No. 5,250,400, Ikenoue et al U.S. Pat. No. 5,254,446, Krishnamurthy et al U.S. Pat. No. 5,262,292, Matsuoka et al U.S. Pat. No. 5,300,407, Romanet et al U.S. Pat. No. 5,302,496, Daifuku et al U.S. Pat. No. 5,336,593, Singer et al U.S. Pat. No. 5,350,667, Tang U.S. Pat. No. 5,395,968, Helling et al U.S. Pat. No. 5,354,826, Tang et al U.S. Pat. No. 5,358,829, Ishidai et al U.S. Pat. No. 5,368,998, Krishnamurthy et al U.S. Pat. No. 5,378,587, Mizukawa et al U.S. Pat. No. 5,409,808, Signer et al U.S. Pat. No. 5,411,841, Wolff U.S. Pat. No. 5,418,123, Tang U.S. Pat. No. 5,424,179, Numata et al EPO 0 257 854, Bowne et al EPO 0 284 240, Webb et al EPO 0 341 204, Miura et al EPO 347,235, Yukio et al EPO 365,252, Yamazaki et al EPO 0 422 595, Kei EPO 0 428 899, Tadahisa et al EPO 0 428 902, Hieechi et al EPO 0 459 331, Sakanoue et al EPO 0 467 327, Kida et al, EPO 0 476 949, Kei et al, EPO 0 487 081, Wolfe EPO 0 489 333, Coraluppi et al EPO 0 512 304, Hirabayashi et al EPO 0 515 128, Harabayashi et at EPO 0 534 703, Sato et al EPO 0 554 778, Tang et al EPO 0 558 145, Mizukawa et al EPO 0 571 959, Schofield et al EPO 0 583 832, Schofield et al EPO 0 583 834, Hirabayashi et al EPO 0 584 793, Tang et al EPO 0 602 748, Tang et al EPO 0 602 749, Lau et al EPO 0 605 918, Allway EPO 0 622 672, Allway EPO 0 622 673, Kita et al EPO 0 629 912, Kapp et al EPO 0 646 841, Kita et al EPO 0 656 561, Ishidai et al EPO 0 660 177, Tanaka et al EPO 0 686 872, Thomas et al WO 90/10253, Williamson et al WO 92/09010, Leyshon et al, WO 92/10788, Crawley et al WO 92/12464, Williamson WO 93/01523, Merkel et al WO 93/02392, Krishnamurthy et al WO 93/02393, Williamson WO 93/07534, UK Patent Application 2,244,053, Japanese Patent Application 03192-350, Renner German OLS 3,624,103, Wolff et al German OLS 3,912,265, and Werner et al German OLS 40 08 067; and
Compounds useful for forming yellow colored dyes upon coupling with oxidized color developer include, for example, Weissberger U.S. Pat. No. 2,298,443, Okumura et al U.S. Pat. No. 4,022,620, Buckland et al U.S. Pat. No. 4,758,501, Ogawa et al U.S. Pat. No. 4,791,050, Buckland et al U.S. Pat. No. 4,824,771, Sato et al U.S. Pat. No. 4,824,773, Renner et al U.S. Pat. No. 4,855,222, Tsoi U.S. Pat. No. 4,978,605, Tsuruta et al U.S. Pat. No. 4,992,360, Tomotake et al U.S. Pat. No. 4,994,361, Leyshon et al U.S. Pat. No. 5,021,333, Masukawa U.S. Pat. No. 5,053,325, Kubota et al U.S. Pat. No. 5,066,574, Ichijima et al U.S. Pat. No. 5,066,576, Tomotake et al U.S. Pat. No. 5,100,773, Lau et al U.S. Pat. No. 5,118,599, Kunitz U.S. Pat. No. 5,143,823, Kobayashi et al U.S. Pat. No. 5,187,055, Crawley U.S. Pat. No. 5,190,848, Motoki et al U.S. Pat. No. 5,213,958, Tomotake et al U.S. Pat. No. 5,215,877, Tsoi U.S. Pat. No. 5,215,878, Hayashi U.S. Pat. No. 5,217,857, Takada et al U.S. Pat. No. 5,219,716, Ichijima et al U.S. Pat. No. 5,238,803, Kobayashi et al U.S. Pat. No. 5,283,166, Kobayashi et al U.S. Pat. No. 5,294,531, Mihayashi et al U.S. Pat. No. 5,306,609, Fukuzawa et al U.S. Pat. No. 5,328,818, Yamamoto et al U.S. Pat. No. 5,336,591, Saito et al U.S. Pat. No. 5,338,654, Tang et al U.S. Pat. No. 5,358,835, Tang et al. U.S. Pat. No. 5,358,838, Tang et al U.S. Pat. No. 5,360,713, Morigaki et al U.S. Pat. No. 5,362,617, Tosaka et al U.S. Pat. No. 5,382,506, Ling et al U.S. Pat. No. 5,389,504, Tomotake et al U.S. Pat. No. 5,399,474, Shibata U.S. Pat. No. 5,405,737, Goddard et al U.S. Pat. No. 5,411,848, Tang et al U.S. Pat. No. 5,427,898, Himmelmann et al EPO 0 327 976, Clark et al EPO 0 296 793, Okusa et al EPO 0 365 282, Tsoi EPO 0 379 309, Kida et al EPO 0 415 375, Mader et al EPO 0 437 818, Kobayashi et al EPO 0 447 969, Chino et al EPO 0 542 463, Saito et al EPO 0 568 037, Tomotake et al EPO 0 568 196, Okumura et al EPO 0 568 777 and Yamada et al EPO 0 570 006, Kawai EPO 0 573 761, Carmack et al EPO 0 608 956, Carmack et al EPO 0 608 957, Mooberry et al EPO 0 628 865.
Photographic elements of the present invention may also usefully include a magnetic recording material as described in Research Disclosure, Item 34390, November 1992, or a transparent magnetic recording layer such as a layer containing magnetic particles on the underside of a transparent support as in U.S. Pat. No. 4,279,945 and U.S. Pat. No. 4,302,523. The element typically will have a total thickness (excluding the support) of from 5 to 30 microns. While the order of the color sensitive layers can be varied, they will normally be red-sensitive, green-sensitive and blue-sensitive, in that order on a transparent support, (that is, blue sensitive furthest from the support).
The present invention also contemplates the use of photographic elements of the present invention in what are often referred to as single use cameras (or xe2x80x9cfilm with lensxe2x80x9d units). Single use cameras are well known and typically comprise (1) a plastic inner camera shell including a taking lens, a film metering mechanism, and a simple shutter and (2) a paper-cardboard outer sealed pack which contains the inner camera shell and has respective openings for the taking lens and for a shutter release button, a frame counter window, and a film advance thumbwheel on the camera shell. The camera may also have a flash unit to provide light when the picture is taken. The inner camera shell has front and rear viewfinder windows located at opposite ends of a see-through viewfinder tunnel, and the outer sealed pack has front and rear openings for the respective viewfinder windows. At the manufacturer, the inner camera shell is loaded with a film cartridge, and substantially the entire length of the unexposed filmstrip is factory prewound from the cartridge into a supply chamber of the camera shell. After the customer takes a picture, the thumbwheel is manually rotated to rewind the exposed frame into the cartridge. The rewinding movement of the filmstrip the equivalent of one frame rotates a metering sprocket to decrement a frame counter to its next lower numbered setting. When substantially the entire length of the filmstrip is exposed and rewound into the cartridge, the single-use camera is sent to a photofinisher who first removes the inner camera shell from the outer sealed pack and then removes the filmstrip from the camera shell. The filmstrip is processed, and the camera shell and the opened pack are thrown away.
In the following discussion of suitable materials for use in elements of this invention, reference will be made to Research Disclosure I, The foregoing references and all other references cited in this application, are incorporated herein by reference.
The silver halide emulsions employed in the photographic elements of the present invention may be negative-working, such as surface-sensitive emulsions or unfogged internal latent image forming emulsions, or positive working emulsions of the internal latent image forming type (that are fogged during processing). Suitable emulsions and their preparation as well as methods of chemical and spectral sensitization are described in Sections I through V. Color materials and development modifiers are described in Sections V through XX. Vehicles which can be used in the photographic elements are described in Section II, and various additives such as brighteners, antifoggants, stabilizers, light absorbing and scattering materials, hardeners, coating aids, plasticizers, lubricants and matting agents are described, for example, in Sections VI through XIII. Manufacturing methods are described in all of the sections, layer arrangements particularly in Section M, exposure alternatives in Section XVI, and processing methods and agents in Sections XIX and XX.
With negative working silver halide a negative image can be formed. Optionally a positive (or reversal) image can be formed although a negative image is typically first formed.
The photographic elements of the present invention may also use colored couplers (e.g. to adjust levels of interlayer correction) and masking couplers such as those described in EP 213 490; Japanese Published Application 58-172,647; U.S. Pat. No. 2,983,608; German Application DE 2,706,117C; U.K. Patent 1,530,272; Japanese Application A-113935; U.S. Pat. No. 4,070,191 and German Application DE 2,643,965. The masking couplers may be shifted or blocked.
The photographic elements may also contain materials that accelerate or otherwise modify the processing steps of bleaching or fixing to improve the quality of the image. Bleach accelerators described in EP 193 389; EP 301 477; U.S. Pat. No. 4,163,669; U.S. Pat. No. 4,865,956; and U.S. Pat. No. 4,923,784 are particularly useful. Also contemplated is the use of nucleating agents, development accelerators or their precursors (UK Patent 2,097,140; U.K. Patent 2,131,188); development inhibitors and their precursors (U.S. Pat. No. 5,460,932; U.S. Pat. No. 5,478,711); electron transfer agents (U.S. Pat. No. 4,859,578; U.S. Pat. No. 4,912,025); antifogging and anti color-mixing agents such as derivatives of hydroquinones, aminophenols, amines, gallic acid; catechol; ascorbic acid; hydrazides; sulfonamidophenols; and non color-forming couplers.
The elements may also contain filter dye layers comprising colloidal silver sol or yellow and/or magenta filter dyes and/or antihalation dyes (particularly in an undercoat beneath all light sensitive layers or in the side of the support opposite that on which all light sensitive layers are located) either as oil-in-water dispersions, latex dispersions or as solid particle dispersions. Additionally, they may be used with xe2x80x9csmearingxe2x80x9d couplers (e.g. as described in U.S. Pat. No. 4,366,237, EP 096 570; U.S. Pat. No. 4,420,556, and U.S. Pat. No. 4,543,323. ) Also, the couplers may be blocked or coated in protected form as described, for example, in Japanese Application 61/258,249 or U.S. Pat. No. 5,019,492.
The photographic elements may further contain other image-modifying compounds such as xe2x80x9cDevelopment Inhibitor-Releasingxe2x80x9d compounds (DIR""s). Useful additional DIR""s for elements of the present invention, are known in the art and examples are described in U.S. Pat. Nos. 3,137,578, 3,148,022; 3,148,062; 3,227,554; 3,384,657; 3,379,529; 3,615,506; 3,617,291; 3,620,746; 3,701,783; 3,733,201; 4,049,455; 4,095,984; 4,126,459; 4,149,886; 4,150,228; 4,211,562; 4,248,962; 4,259,437; 4,362,878; 4,409,323; 4,477,563; 4,782,012; 4,962,018; 4,500,634; 4,579,816; 4,607,004; 4,618,571; 4,678,739; 4,746,600; 4,746,601; 4,791,049; 4,857,447; 4,865,959; 4,880,342, 4,886,736; 4,937,179, 4,946,767; 4,948,716; 4,952,485; 4,956,269; 4,959,299; 4,966,835; 4,985,336 as well as in patent publications GB 1,560,240, GB 2,007,662, GB 2,032,914; GB 2,099,167; DE 2,842,063, DE 2,937,127; DE 3,636,824; DE 3,644,416 as well as the following European Patent Publications: 272,573; 335,319; 336,411, 346,899; 362,870; 365,252; 365,346; 373,382; 376,212; 377,463; 378,236; 384,670; 396,486; 401,612, 401,613.
DIR compounds are also disclosed in xe2x80x9cDeveloper-Inhibitor-Releasing (DIR) Couplers for Color Photography,xe2x80x9d C. R. Barr, J. R. Thirtle and P. W. Vittum in Photographic Science and Engineering, Vol. 13, p. 174 (1969), incorporated herein by reference.
The type of silver halide grains to be used in the practice of this invention may include polymorphic, cubic, and octahedral. The grain size of the silver halide may have any distribution known to be useful in photographic compositions, and may be either polydipersed or monodispersed.
Preferably, tabular grain silver halide emulsions may be used in the practice of this invention. Tabular grains are those with two parallel major faces each clearly larger than any remaining grain face and tabular grain emulsions are those in which the tabular grains account for at least 50 percent, preferably  greater than 70 percent and optimally  greater than 90 percent of total grain projected area. The tabular grains can account for substantially all ( greater than 97 percent) of total grain projected area. The tabular grain emulsions can be high aspect ratio tabular grain emulsionsxe2x80x94i.e., ECD/t greater than 8, where ECD is the diameter of a circle having an area equal to grain projected area and t is tabular grain thickness; intermediate aspect ratio tabular grain emulsionsxe2x80x94i.e., ECD/t=5 to 8, or low aspect ratio tabular grain emulsionsxe2x80x94i.e., ECD/t=2 to 5. The emulsions typically exhibit high tabularity (T), where T (i.e., ECD/t2) greater than 25 and ECD and t are both measured in micrometers (xcexcm). The tabular grains can be of any thickness compatible with achieving an aim average aspect ratio and/or average tabularity of the tabular grain emulsion. Preferably the tabular grains satisfying projected area requirements are those having thicknesses of  less than 0.3 xcexcm, thin ( less than 0.2 xcexcm) tabular grains being specifically preferred and ultrathin ( less than 0.07 xcexcm) tabular grains being contemplated for maximum tabular grain performance enhancements.
Tabular grains formed of silver halide(s) that form a face centered cubic (rock salt type) crystal lattice structure can have either {100} or {111} major faces. Emulsions containing {111 } major face tabular grains, including those with controlled grain dispersities, halide distributions, twin plane spacing, edge structures and grain dislocations as well as adsorbed {111} grain face stabilizers, are illustrated in those references cited in Research Disclosure I, Section I.B.(3) (page 503).
The silver halide used in the photographic element of the present invention may be silver iodobromide, silver bromide, silver chloride, silver chlorobromide, silver chlorolodobromide, and the like.
The silver halide grains to be used in the invention may be prepared according to methods known in the art, such as those described in Research Disclosure I and James, The Theory of the Photographic Process. These include methods such as ammoniacal emulsion making, neutral or acidic emulsion making, and others known in the art. These methods generally involve mixing a water soluble silver salt with a water soluble halide salt in the presence of a protective colloid, and controlling the temperature, pAg, pH values, etc, at suitable values during formation of the silver halide by precipitation.
In the course of grain precipitation one or more dopants (grain occlusions other than silver and halide) can be introduced to modify grain properties. For example, any of the various conventional dopants disclosed in Research Disclosure, Item 36544, Section I. Emulsion grains and their preparation, sub-section G. Grain modifying conditions and adjustments, paragraphs (3), (4) and (5), can be present in the emulsions of the invention. Doping with selenium or with selenium and iridium as described in Johnson and Wightman U.S. Pat. No. 5,164,292 may be particularly beneficial. In addition it is specifically contemplated to dope the grains with transition metal hexacoordination complexes containing one or more organic ligands, as taught by Olm et al U.S. Pat. No. 5,360,712, the disclosure of which is here incorporated by reference.
It is specifically contemplated to incorporate in the face centered cubic crystal lattice of the grains a dopant capable of increasing imaging speed by forming a shallow electron trap (hereinafter also referred to as a SET) as discussed in Research Discolosure Item 36736 published November 1994, here incorporated by reference.
The SET dopants are effective at any location within the grains. Generally better results are obtained when the SET dopant is incorporated in the exterior 50 percent of the grain, based on silver. An optimum grain region for SET incorporation is that formed by silver ranging from 50 to 85 percent of total silver forming the grains. The SET can be introduced all at once or run into the reaction vessel over a period of time while grain precipitation is continuing. Generally SET forming dopants are contemplated to be incorporated in concentrations of at least 1xc3x9710xe2x88x927 mole per silver mole up to their solubility limit, typically up to about 5xc3x9710xe2x88x924 mole per silver mole.
SET dopants are known to be effective to reduce reciprocity failure. In particular the use of iridium hexacoordination complexes or Ir+4 complexes as SET dopants is advantageous.
Iridium dopants that are ineffective to provide shallow electron traps (non-SET dopants) can also be incorporated into the grains of the silver halide grain emulsions to reduce reciprocity failure. To be effective for reciprocity improvement the Ir can be present at any location within the grain structure. A preferred location within the grain structure for Ir dopants to produce reciprocity improvement is in the region of the grains formed after the first 60 percent and before the final 1 percent (most preferably before the final 3 percent) of total silver forming the grains has been precipitated. The dopant can be introduced all at once or run into the reaction vessel over a period of time while grain precipitation is continuing. Generally reciprocity improving non-SET Ir dopants are contemplated to be incorporated at their lowest effective concentrations.
Although generally preferred concentration ranges for the various SET and non-SET Ir dopants have been set out above, it is recognized that specific optimum concentration ranges within these general ranges can be identified for specific applications by routine testing. It is specifically contemplated to employ the SET and non-SET Ir dopants singly or in combination. For example, grains containing a combination of an SET dopant and a non-SET Ir dopant are specifically contemplated.
The photographic elements of the present invention, as is typical, provide the silver halide in the form of an emulsion. Photographic emulsions generally include a vehicle for coating the emulsion as a layer of a photographic element. Useful vehicles include both naturally occurring substances such as proteins, protein derivatives, cellulose derivatives (e.g., cellulose esters), gelatin (e.g., alkali-treated gelatin such as cattle bone or hide gelatin, or acid treated gelatin such as pigskin gelatin), deionized gelatin, gelatin derivatives (e.g., acetylated gelatin, phthalated gelatin, and the like), and others as described in Research Disclosure I. Also useful as vehicles or vehicle extenders are hydrophilic water-permeable colloids. These include synthetic polymeric peptizers, carriers, and/or binders such as poly(vinyl alcohol), poly(vinyl lactams), acrylamide polymers, polyvinyl acetals, polymers of alkyl and sulfoalkyl acrylates and methacrylates, hydrolyzed polyvinyl acetates, polyamides, polyvinyl pyridine, methacrylamide copolymers, and the like, as described in Research Disclosure I. The vehicle can be present in the emulsion in any amount useful in photographic emulsions. The emulsion can also include any of the addenda known to be useful in photographic emulsions.
The silver halide to be used in the invention may be advantageously subjected to chemical sensitization. Compounds and techniques useful for chemical sensitization of silver halide are known in the art and described in Research Disclosure I and the references cited therein. Compounds useful as chemical sensitizers, include, for example, active gelatin, sulfur, selenium, tellurium, gold, platinum, palladium, iridium, osmium, rhenium, phosphorous, or combinations thereof. Chemical sensitization is generally carried out at pAg levels of from 5 to 10, pH levels of from 4 to 8, and temperatures of from 30 to 80xc2x0 C., as described in Research Disclosure I, Section IV (pages 510-511) and the references cited therein.
The silver halide may be sensitized by sensitizing dyes by any method known in the art, such as described in Research Disclosure I. The dye may be added to an emulsion of the silver halide grains and a hydrophilic colloid at any time prior to (e.g., during or after chemical sensitization) or simultaneous with the coating of the emulsion on a photographic element. The dyes may, for example, be added as a solution in water or an alcohol. The dye/silver halide emulsion may be mixed with a dispersion of color image-forming coupler immediately before coating or in advance of coating (for example, 2 hours).
A summary of useful spectral sensitizing dyes is contained in Research Disclosure 308119, Section V. Also of interest are sensitizing dyes disclosed in U.S. Pat. Nos. 4,439,520, 4,581,329; 4,582,786; 4,592,621; 4,609,621, 4,675,279; 4,678,741; 4,720,451; 4,818,675; 4,945,036; and 4,952,491, the entire disclosures thereof are incorporated herein by reference.
Preferred red sensitizing dyes include, for example:
Anhydro-5,5xe2x80x2-dichloro-9-ethyl-3,3xe2x80x2-di-(3-sulfopropyl)thiacarbocyanine hydroxide, triethylammonium salt,
Anhydro-9-ethyl-5xe2x80x2,6xe2x80x2-dimethoxy-5-phenyl-3-(3-sulfobutyl)-3xe2x80x2-(3-sulfopropyl)oxatbiacarbocyanine hydroxide;
Anhydro-9-ethyl-5,5xe2x80x2-dimethyl-3,3xe2x80x2-di-(3-sulfopropyl) thiacarbocyanine hydroxide, triethylammonium salt;
Anhydro-9-ethyl-5xe2x80x2,6xe2x80x2-dimethyl-5-phenyl-3-(2-sulfoethyl)-3xe2x80x2-(4-sulfobutyl)oxathiacarbocyanine hydroxide, sodium salt;
Anhydro-11-ethyl-1,1xe2x80x2-di-(3-sulfopropyl)naphtho[1,2-d] thiazolocarbocyanine hydroxide, triethylammonium salt;
Anhydro-5,5-dichloro-3,9-diethyl-3xe2x80x2-(3-sulfopropyl)thiacarbocyanine hydroxide,
Anhydro-5,6-dichloro-1-ethyl-1xe2x80x2,3-di-(3-sulfopropyl) benzimidazolonaphtho[1,2-d]thiazolocarbocyanine hydroxide, triethylammonium salt;
3,3xe2x80x2-Di-(2-carboxyethyl)-5,5xe2x80x2-dichloro-9-ethylthiacarbocyanine bromide;
Anhydro-9-ethyl-3-methyl-S-phenyl-3xe2x80x2-(3-sulfopropyl) oxaselenacarbocyanine hydroxide;
2,4,6(1H,3H,5H)-Pyrimidinetrione, 5-(2-(1-ethylnaphtho[1,2-d]thiazol-2(3H)-ylidene)-1-((1-ethylnaphtho[1,2-d]thiazol-2(3H)-ylidene)methyl)ethylidene)-1,3-bis-(2-methoxyethyl)-1,1xe2x80x2,11-triethylnaphtho[1,2-d]thiazolocarbocyanine bromide;
Anhydro-3,9-diethyl-5,5xe2x80x2-dimethoxy-3-(3-sulfopropyl)thiacarbocyanine hydroxide,
Anhydro-9-ethyl-5,6-dimethoxy-5xe2x80x2-phenyl-3,3xe2x80x2-di-(3-sulfopropyl)thiacarbocyanine hydroxide, potassium salt;
Anhydro-9-ethyl-5xe2x80x2,6xe2x80x2-dimethoxy-5-phenyl-3,3xe2x80x2-di-(3-Sulfopropyl)oxathiacarbocyanine hydroxide, sodium salt;
2-(2-(4-diethylaminophenyl)ethenyl)benzothiazole
Anhydro-9-ethyl-5,6-dimethyl-3-(2-sulfoethyl)-3xe2x80x2-(3-sulfopropyl)naphtho[1,2-d]thiazolooxacarbocyanine hydroxide, tetramethyguanidinium salt;
Anhydro-5,5xe2x80x2-dichloro-9-ethyl-3,3xe2x80x2-di-(3-(2-hydroxysulfopropyl))thiacarbocyanine hydroxide, triethylammonium salt;
Anhydro-3-ethyl-9,11-neopentylene-3xe2x80x2-(3-sulfopropyl)thiadicarbocyanine hydroxide;
3,3xe2x80x2-diethyl-9,11-neopentylene-thiadicarbocyanine p-toluenesulfonate;
3,3xe2x80x2-di-(2-hydroxyethyl) thiadicarbocyanine bromide.
Preferred green sensitizing dyes are, for example:
Anhydro-5-chloro-9-ethyl-5xe2x80x2-phenyl-3xe2x80x2-(3-sulfobutyl)-3-(3-sulfopropyl)oxacarbocyanine hydroxide, triethylammonium salt;
Anhydro-6,6xe2x80x2-dichloro-1,1xe2x80x2-diethyl-3,3xe2x80x2-di-(3-sulfbpropyl)-5,5xe2x80x2bis(trifluoromethyl)benzimidazolocarbocyanine hydroxide, triethylammonium salt;
Anhydro-11-ethyl-1,1xe2x80x2-di-(3-sulfopropyl)naphth[1,2-d]oxazolocarbocyanine hydroxide, triethylammonium salt;
Anhydro-5-chloro-9-ethyl-5xe2x80x2-phenyl-3xe2x80x2-(2-sulfoethyl)-3-(3-sulfopropyl)oxacarbocyanine hydroxide, triethylammonium salt;
Anhydro-6,6xe2x80x2-dichloro-1,1xe2x80x2-diethyl-3,3xe2x80x2-di-(4-sulfobutyl)-5,5xe2x80x2-bis(trifluoromethyl)benzimidazolocarbocyanine hydroxide, triethylammonium salt;
Anhydro-9-ethyl-5,5xe2x80x2-diphenyl-3,3xe2x80x2-di-(2-sulfoethyl) oxacarbocyanine hydroxide, sodium salt;
Anhydro-9-ethyl-5-t-pentyl-5xe2x80x2-phenyl-3-(4-sulfobutyl)-3xe2x80x2-(2-sulfoethyl) oxacarbocyanine hydroxide, triethylammonium salt;
Anhydro-9-ethyl-5,5xe2x80x2-diphenyl-3,3xe2x80x2-di-(4-sulfobutyl) oxacarbocyanine hydroxide, sodium salt;
5,5-Dicyano-1,1xe2x80x2,3-triethyl-3xe2x80x2-(4-acetylsulfamoylbutyl) benzimidazolocarbocyanine bromide;
Anhydro-9-ethyl-5,5xe2x80x2-diphenyl-3,3xe2x80x2-di-(3-sulfobutyl)oxacarbocyanine hydroxide, sodium salt;
Anhydro-9-ethyl-5,5xe2x80x2-dichloro-3,3xe2x80x2-di-(3-sulfopropyl)oxacarbocyanine hydroxide, triethylammonium salt;
Anhydro-5,5xe2x80x2,6,6xe2x80x2-tetrachloro-1,1xe2x80x2,3-triethyl-3-(3-sulfopropyl)benzimidazolocarbocyanine hydroxide;
Anhydro-3,9-diethyl-5-phenyl-3xe2x80x2-(3-sulfopropyl)oxacarbocyanine hydroxide,
Anhydro-9-ethyl-5,5xe2x80x2-diphenyl-3,3xe2x80x2-di-(3-sulfopropyl) oxacarbocyanine hydroxide, sodium salt;
Anhydro-5-chloro-9-ethyl-5xe2x80x2-phenyl-3,3-di-(3-sulfopropyl) oxacarbocyanine hydroxide, triethylammonium salt;
Anhydro-9-ethyl-5,5xe2x80x2-diphenylcarbamoyl-3,3xe2x80x2-di-(3-sulfopropyl)oxacarbocyanine hydroxide, triethylammonium salt;
Anhydro-9-ethyl-3xe2x80x2-ethyl-3-[(N-methylsulfonyl)carbamoylmethyl]-5xe2x80x2-phenyloxathiacarbocyanine hydroxide;
Anhydro-9-ethyl-3xe2x80x2-ethyl-3-[(N-methylsulfonyl)carbamoylmethyl]-5xe2x80x2-phenyl-(3xe2x80x2-sulfopropyl) oxathiacarbocyanine hydroxide, triethylammonium salt.
Preferred blue sensitizing dyes include, for example:
Anhydro-5,5xe2x80x2-dichloro-3,3xe2x80x2-di-(3-sulfopropyl)thiacyanine hydroxide, triethylammonium. salt;
Anhydro-5,5xe2x80x2-dichloro-3,3xe2x80x2-di-(4-sulfobutyl)thiacyanine hydroxide, triethylammonium salt;
Anhydro-5,5xe2x80x2-dimethoxy-3,3xe2x80x2-di-(4-sulfobutyl)thiacyanine hydroxide, triethylammonium salt;
Anhydro-5-chloro-3,3xe2x80x2-di-(3-sulfopropyl)naphtho[1,2-d]thiazolothiacyanine hydroxide, triethylammonium salt,
Anhydro-5-chloro-5xe2x80x2-phenyl-3,3xe2x80x2-di-(3-sulfopropyl)oxathiacyanine hydroxide, triethylammonium salt;
Anhydro-5-chloro-5xe2x80x2-(pyrrole-1-yl)-3,3xe2x80x2-di-(3-sulfopropyl)thiacyanine hydroxide, triethylammonium salt. Photographic elements of the present invention are preferably imagewise exposed using any of the known techniques, including those described in Research Disclosure I, section XVI. This typically involves exposure to light in the visible region of the spectrum, and typically such exposure is of a live image through a lens, although exposure can also be exposure to a stored image (such as a computer stored image) by means of light emitting devices (such as light emitting diodes, CRT and the like).
Photographic elements comprising the composition of the invention can be processed in any of a number of well-known photographic processes utilizing any of a number of well-known processing compositions, described, for example, in Research Disclosure I, or in T. H. James, editor, The Theory of the Photographic Process, 4th Edition, Macmillan, N.Y., 1977. In the case of processing a negative working element, the element is treated with a color developer (that is one which will form the colored image dyes with the color couplers), and then with a oxidizer and a solvent to remove silver and silver halide. In the case of processing a reversal color element, the element is first treated with a black and white developer (that is, a developer which does not form colored dyes with the coupler compounds) followed by a treatment to fog silver halide (usually chemical fogging or light fogging), followed by treatment with a color developer. Preferred color developing agents are p-phenylenediamines. Especially preferred are:
4-amino N,N-diethylaniline hydrochloride,
4-amino-3-methyl-N,N-diethylaniline hydrochloride,
4-amino-3-methyl-N-ethyl-N-(xcex2-(methanesulfonamido) ethylaniline sesquisulfate hydrate,
4-amino-3-methyl-N-ethyl-N-(xcex2-hydroxyethyl)aniline sulfate,
4-amino-3-xcex2-(methanesulfonamido)ethyl-N,N-diethylaniline hydrochloride and
4-amino-N-ethyl-N-(2-methoxyethyl)-m-toluidine di-p-toluene sulfonic acid.
Dye images can be formed or amplified by processes which employ in combination with a dye-image-generating reducing agent an inert transition metal-ion complex oxidizing agent, as illustrated by Bissonette U.S. Pat. Nos. 3,748,138, 3,826,652, 3,862,842 and 3,989,526 and Travis U.S. Pat. No. 3,765,891, and/or a peroxide oxidizing agent as illustrated by Matejec U.S. Pat. No. 3,674,490, Research Disclosure, Vol. 116, December, 1973, Item 11660, and Bissonette Research Disclosure, Vol. 148, August, 1976, Items 14836, 14846 and 14847. The photographic elements can be particularly adapted to form dye images by such processes as illustrated by Dunn et al U.S. Pat. No. 3,822,129, Bissonette U.S. Pat. Nos. 3,834,907 and 3,902,905, Bissonette et al U.S. Pat. No. 3,847,619, Mowrey U.S. Pat. No. 3,904,413, Hirai et al U.S. Pat. No. 4,880,725, Iwano U.S. Pat. No. 4,954,425, Marsden et al U.S. Pat. No. 4,983,504, Evans et al U.S. Pat. No. 5,246,822, Twist U.S. Pat. No. No. 5,324,624, Fyson EPO 0 487 616, Tannahill et al WO 90/13059, Marsden et al WO 90/13061, Grimsey et al WO 91/16666, Fyson WO 91/17479, Marsden et al WO 92/01972. Tannahill WO 92/05471, Henson WO 92/07299, Twist WO 93/01524 and WO 93/11460 and Wingender et al German OLS 4,211,460.
Development is followed by bleach-fixing, to remove silver or silver halide, washing and drying.
The photographic elements of this invention may be processed utilizing either conventional processing systems, described above or low volume processing systems.
Low volume systems are those where film processing is initiated by contact to a processing solution, but where the processing solution volume is comparable to the total volume of the imaging layer to be processed. This type of system may include the addition of non-solution processing aids, such as the application of heat or of a laminate layer that is applied at the time of processing. Conventional photographic systems are those where film elements are processed by contact with conventional photographic processing solutions, and the volume of such solutions is very large in comparison to the volume of the imaging layer.
Low volume processing is defined as processing where the volume of applied developer solution is between about 0.1 to about 10 times, preferably about 0.5 to about 10 times, the volume of solution required to swell the photographic element. This processing may take place by a combination of solution application, external layer lamination, and heating. The low volume system photographic element may receive some or all of the following treatments:
(I) Application of a solution directly to the film by any means, including spray, inkjet, coating, gravure process and the like.
(II) Soaking of the film in a reservoir containing a processing solution. This process may also take the form of dipping or passing an element through a small cartridge.
(III) Lamination of an auxiliary processing element to the imaging element. The laminate may have the purpose of providing processing chemistry, removing spent chemistry, or transferring image information from the latent image recording film element. The transferred image may result from a dye, dye precursor, or silver containing compound being transferred in a image-wise manner to the auxiliary processing element.
(IV) Heating of the element by any convenient means, including a simple hot plate, iron, roller, heated drum, microwave heating means, heated air, vapor, or the like. Heating may be accomplished before, during, after, or throughout any of the preceding treatments I-III. Heating may cause processing temperatures ranging from room temperature to 100xc2x0 C.
Photographic elements and methods of processing such elements particularly suitable for use with this invention are described in Research Disclosure, February 1995, Item 37038, incorporated herein by reference.
The processed photographic elements of this invention may serve as origination material for some or all of the following processes: image scanning to produce an electronic rendition of the capture image, and subsequent digital processing of that rendition to manipulate, store, transmit, output, or display electronically that image. A number of modifications of color negative elements have been suggested for accommodating scanning, as illustrated by Research Disclosure, I Section XIV. Scan facilitating features Research Disclosure, and Research Disclosure September 1994, Item 36544. These systems are contemplated for use in the practice of this invention. Further examples of such processes and useful film features are also described in U.S. Pat. No. 5,840,470, U.S. Pat. No. 6,045,938; U.S. Pat. No. 6,021,277; EP 961,482 and EP905,651.
For example, it is possible to scan the photographic element successively within the blue, green, and red regions of the spectrum or to incorporate blue, green, and red light within a single scanning beam that is divided and passed through blue, green, and red filters to form separate scanning beams for each color record. A simple technique is to scan the photographic element point-by-point along a series of laterally offset parallel scan paths. The intensity of light passing through the element at a scanning point is noted by a sensor, which converts radiation received into an electrical signal. Most generally this electronic signal is further manipulated to form a useful electronic record of the image. For example, the electrical signal can be passed through an analog-to-digital converter and sent to a digital computer together with location information required for pixel (point) location within the image. In another embodiment, this electronic signal is encoded with calorimetric or tonal information to form an electronic record that is suitable to allow reconstruction of the image into viewable forms such as computer monitor displayed images, television images, printed images, and so forth.
It is contemplated that many of imaging elements of this invention will be scanned prior to the removal of silver halide from the element. The remaining silver halide yields a turbid coating, and it is found that improved scanned image quality for such a system can be obtained by the use of scanners that employ diffuse illumination optics. Any technique known in the art for producing diffuse illumination can be used. Preferred systems include reflective systems, that employ a diffusing cavity whose interior walls are specifically designed to produce a high degree of diffuse reflection, and transmissive systems, where diffusion of a beam of specular light is accomplished by the use of an optical element placed in the beam that serves to scatter light. Such elements can be either glass or plastic that either incorporate a component that produces the desired scattering, or have been given a surface treatment to promote the desired scattering.
One of the challenges encountered in producing images from information extracted by scanning is that the number of pixels of information available for viewing is only a fraction of that available from a comparable classical photographic print. It is, therefore, even more important in scan imaging to maximize the quality of the image information available. Enhancing image sharpness and minimizing the impact of aberrant pixel signals (i.e., noise) are common approaches to enhancing image quality. A conventional technique for minimizing the impact of aberrant pixel signals is to adjust each pixel density reading to a weighted average value by factoring in readings from adjacent pixels, closer adjacent pixels being weighted more heavily. The elements of the invention can have density calibration patches derived from one or more patch areas on a portion of unexposed photographic recording material that was subjected to reference exposures, as described by Wheeler et al U.S. Pat. No. 5,649,260, Koeng at al U.S. Pat. No. 5,563,717, Cosgrove et al U.S. Pat. No. 5,644,647, and Reem and Sutton U.S. Pat. No. 5,667,944.
Illustrative systems of scan signal manipulation, including techniques for maximizing the quality of image records, are disclosed by Bayer U.S. Pat. No. 4,553,156; Urabe et al U.S. Pat. No. 4,591,923, Sasaki et al U.S. Pat. No. 4,631,578; Alkofer U.S. Pat. No. 4,654,722; Yamada et al U.S. Pat. No. 4,670,793, Klees U.S. Pat. Nos. 4,694,342 and 4,962,542; Powell U.S. Pat. No. 4,805,031; Mayne et al U.S. Pat. No. 4,829,370; Abdulwabab U.S. Pat. No. 4,839,721; Matsunawa et al U.S. Pat. Nos. 4,841,361 and 4,937,662; Mizukoshi et al U.S. Pat. No. 4,891,713; Petilli U.S. Pat. No. 4,912,569, Sullivan et al U.S. Pat. Nos. 4,920,501 and 5,070,413; Kimoto et al U.S. Pat. No. 4,929,979; Hirosawa et al U.S. Pat. No. 4,972,256; Kaplan U.S. Pat. No. 4,977,521; Sakai U.S. Pat. No. 4,979,027; Ng U.S. Pat. No. 5,003,494; Katayama et al U.S. Pat. No. 5,008,950; Kimura et al U.S. Pat. No. 5,065,255; Osamu et al U.S. Pat. No. 5,051,842; Lee et al U.S. Pat. No. 5,012,333; Bowers et al U.S. Pat. No. 5,107,346; Telle U.S. Pat. No. 5,105,266; MacDonald et al U.S. Pat. No. 5,105,469; and Kwon et al U.S. Pat. No. 5,081,692. Techniques for color balance adjustments during scanning are disclosed by Moore et al U.S. Pat. No. 5,049,984 and Davis U.S. Pat. No. 5,541,645. Color image reproduction of scenes with color enhancement and preferential tone-scale mapping are described by Burh et al. in U.S. Pat. Nos. 5,300,381 and 5,528,339.
The digital color records once acquired are in most instances adjusted to produce a pleasingly color balanced image for viewing and to preserve the color fidelity of the image bearing signals through various transformations or renderings for outputting, either on a video monitor or when printed as a conventional color print. Preferred techniques for transforming image bearing signals after scanning are disclosed by Giorgianni et al U.S. Pat. No. 5,267,030, the disclosures of which are herein incorporated by reference. The signal transformation techniques of Giorgianni et al ""030 described in connection with FIG. 8 represent a specifically preferred technique for obtaining a color balanced image for viewing.
Further illustrations of the capability of those skilled in the art to manage color digital image information are provided by Giorgianni and Madden Digital Color Management, Addison-Wesley, 1998.